Terms used in this disclosure are explained in definitions included in the invention description. Several such terms, related mainly to novel objects proposed herein, require supplemental explanations for their single-valued interpretation which are offered herein. A P-element is defined as an IO (ion-optical) element that is configured to create a two-dimensional mean geometric surface (M-surface, hereinafter) of the IO element. The M-surface is formed by perpendicular displacement of a generated straight line. In a general case, the P-element may be created from a nonplanar two-dimensional mean surface. Particular embodiments of the P-elements are modes in which they combine geometric mean planes and a plane of electric field symmetry and/or of magnetic field antisymmetry.
The P-elements are divided into cartesian-two-dimensional P-elements and three-dimensional P-elements. All P-elements are considered to be three-dimensional P-elements with the exception of Cartesian-two-dimensional type P-elements having uniform or nonuniform heights, depending only on two coordinate axes in Cartesian coordinates. Cartesian-two-dimensional P-elements are divided into planar-two-dimensional P-elements with geometric mean planes and surface-two-dimensional P-elements, such as a M-surface, which is formed by parallel displacement of the straight-line along the bent line, zigzag line or bent-zigzag line.
Several examples of the P-elements are: cylindrical condensers, P-elements having asymmetrically nonuniform heights in a parallel front-edge arrangement of Cartesian-two-dimensional electrodes, plane condensers, P-elements with axially asymmetric horizontal orientation of electrodes and with symmetrically nonuniform height or uniform height of electrodes arrangement, sectoral magnetic P-elements, and conic P-elements (V-shaped, conic).
Extensions of the M-surface off the field of the P-element at its input and output are referred to respectively as the input and output mean planes of the P-element.
The P-elements extended in either direction are referred to as extended P-elements. Extended P-elements are designed for simultaneous or successive actions on a single path or multipath ion flux at different segments along the length of the extended P-element.
Any IO system or sub-system interacting three or more times with an ion flux, such as single multi-reflectors, and any IO system or sub-system comprising three or more P-elements, may be described using projections on two or three mutually perpendicular characteristic planes, e.g., a base plane, an incremental plane or longitudinal-incremental plane, and a transverse-incremental plane.
The base plane of an incremental IO system or sub-system is a plane that is perpendicular to the linear axes of extended P-elements parallel to each other.
At least three quarters of the components of planar IO systems or sub-systems, also referred to as the supporting portion of planar IO systems or sub-systems, may be located on a single plane, e.g., their supporting plane. The base plane of a planar IO system is a plane parallel to the ion flux between three or more conjoined sections of supporting P-elements of the IO system, such that the ion flux passes from one section to the other, and this base plane has the smallest angle relative to the supporting plane of the IO system.
The incremental plane of the IO system or subsystem is a plane perpendicular to the base plane of the IO system or subsystem.
The IO systems are divided into two-dimensional systems and three-dimensional systems. IO systems configured to provide ion motion, mainly close upon one or around one plane, are typically two-dimensional systems (for example, IO planar systems and R-multi-reflectors of rectilinear reflecting type), while other IO systems are typically three-dimensional systems.
A planar IO system or sub-system (e.g., planar R-multi-reflector or planar control subsystem) is considered to be open (non-closed type), if it is configured to provide an out-of-base-plane arrangement of descending and outgoing branches of ion paths in the IO system or sub-system. IO systems or subsystems of a non-closed type are considered to be single-plane systems or sub-systems provided that the descending and outgoing branches of ion paths are arranged in one plane. Any other IO systems or sub-systems of non-closed type, which do not meet these conditions are considered to be non-coplanar.
An open IO system or sub-system is defined as a system or sub-system with parallel-projective symmetrically non-coplanar input/output, if it is configured to provide arrangement of descending and outgoing branches of ion paths in one or more planes, the arrangement being one of a typical line components of this IO system or sub-system and perpendicular to the IO system or sub-system base plane.
In a multinodal reflecting IO system, e.g., in a control subsystem (reflection or reflection/refraction subsystem) or in a R-multi-reflector, any constituent IO reflection units designed to receive the ion flux entering from the outside of the IO system and to remove the ion flux from the IO system are referred to as the first (or receiving) IO reflection unit and the last (or output) IO reflection unit, respectively. Other IO reflection units of the multimodal reflecting IO system are referred to as mean IO reflection units, or, each IO reflection unit is referred to by its number along the streamline of ion flux. For example, in a two-loop reflecting R-multi-reflector with four IO reflection units, the IO reflection unit located on one diagonal segment of a typical line with the receiving IO reflection unit is referred to as the second reflection unit, and the IO reflection unit located on one diagonal segment of a typical line with the output IO reflection unit is referred to as the third reflection unit.
In general, various mass-spectrometric methods and mass-spectrometers (MS) are known. In general, a mass-spectrometric method provides the following:                a) Ionize the substance sample in an ionic source unit and remove the ion flux (ions) out it and form the ion flux and control its motion, including its mass dispersion by ion masses (mass dispersion by values of ion mass/charge ratios, m/z), with the aid of static or variable components of magnetic and/or electric fields. The fields are typically generated by groups of ion-conducting blocks composed of ion-conducting IB-channels with boundary surfaces and channel IO subsystems (P-elements), each of which is a part of a MS-channel within an IO system (series-connected ion-conducting IB-channels and ionic source IB-channel of ionic source unit).                    At that, the channel IO subsystem of each ion-conducting IB-channel comprises one or more control subsystems, or comprises a curve main axis in a cross-space dispersing mode or in a multi-reflecting mode;                        b) Register ions by means of one or more sensors of a detector system;        c) Control and manage the operations of all blocks of the mass-spectrometer as well as support the data processing by means of a controller-computer system.A mass-spectrometer (MS) to perform mass-spectrometry processes consists in general of the following:        
a) MS-blocks: ionic source unit formed of a group of ion-conducting blocks, composed of a coupling module element and an analyzer-disperser block. The ionic source units include IB-channels with boundary surfaces and channel IO subsystems (P-elements), and each IB-channel of a block is a part of the MS-channel with the IO system, resulting in an ion-conducting IB-channels of ion-conducting blocks together with the ionic source IB-channel of the ionic source unit. The channel IO subsystems (P-elements) comprises one or more IO control subsystems, or comprises a curve main axis in a cross-space dispersing mode or in a multi-reflecting mode;
b) Detector circuit;
c) Controller-computer system. Each IB-channel serves to form and control motions of channel ion flux and includes a channel IO subsystem with one or more IO elements, each of which contains two or more electrodes and one or more boundary surfaces, the surfaces being surfaces of output or surfaces of input and output for channel ion flux. An ionic source type of an IB-channel, also referred to as an IB-channel of an ionic source unit or an ionic source IB-channel, includes surfaces of output, mainly, in coincidence with a boundary electrode of the ionic source IB-channel. An ion-conducting type of IB-channel, also referred to as an IB-channel of an ion-conducting module or an ion-conducting IB-channel, contains boundary surfaces and channel IO subsystems (IO elements), comprising a single control subsystem or more such subsystems; or comprising a curve main axis in a cross-space dispersing mode or in a multi-reflecting mode.
There are multiple alternatives of MS block-structured docking groups depending on specified tasks to be solved by proposed MS means. According to a quantitative module composition of block-structured docking groups, the MS may include different types of MS modularity levels: extended-multimodule and multimodule MS; MS of mean modularity level, medium modular MS and small-section modular MS.
Small-section modular MS are designed to be operated in a single-stage mass-spectrometry process. As such, a MS block-structured docking group is composed of minimum structural elements: a pre-shaping module and a distributing accelerator module. The block-structured docking group of a MS of mean modularity level is composed of a pre-shaping module, a distributing accelerator module and a module of a refinement cell or an ion trapping module.
The block-structured docking group of multimodule MS is composed of a pre-shaping module, a distributing accelerator module, a module of a refinement cell and an ion trapping module. The block-structured docking group of an extended-multimodule MS is composed of a pre-shaping module, a distributing accelerator module, a module of a refinement cell, an ion trapping module, and a module of further ion accumulation trapping.
The MS of mean modularity level including the module of the refinement cell, the multimodule MS, and the extended-multimodule MS allow to carry out molecule structure analyses based on multi-stage, e.g., tandem, mass-spectrometry (MS/MS) or to carry out the spectrometry with multiple-cycle ion accumulation of a certain mass range (MSn).
All known MS, with the exception of parallel multi-channel quadrupole type MS, are single channel, channel-single-path, MS, ensuring simultaneous analysis of only single-path axial ion flux.
Known parallel multi-channel MS, containing, in one vacuum volume, at least several channels, and referred to as parallel MS, comprise a single-stage quadrupole MS. U.S. Pat. No. 7,381,947, Publ. Jun. 3, 2008 describes a single-stage quadrupole MS, including N channels, where N is a integer number greater than one, composed of the following: an ionic source module including N ionic source IB-channels, each of which has a single source of ions; a block-structured docking group provided with a pre-shaping module and a distributing accelerator module, each of which contains N IB-channels; a dispersing analyzer module which contains N dispersing analyzer IB-channels; a detector system, including N ion detectors; and a controller computer system. The dispersing analyzer module comprises N coupled quadrupole IB-channels having common interchannel electrodes, each of which is a single-path (single-flow) channel.
This MS type, just as all known single-stage MS with a quadrupole ion trap, is notable for its poor weighing accuracy, i.e., up to <20 ppm and shows a relatively low resolution power up to several tens of thousands.
The main disadvantage of this MS type is in the low value of resolution power/costs ratio. Moreover, this MS type is related to low-modular MS and does not allow to carry out structure analyses.
Known methods of spectrometry and mass-spectrometer (MS) described in the invention of A. Makarov (Pub. No.: US 2009/0166528 A1, Publ. Jul. 2, 2009) is the closest prototype to the claimed invention. The block-structured docking group of this MS prototype comprises a pre-shaping module, a distributing accelerator module, a refinement cell, and a module of ion trapping. Some MS versions optionally comprise a module of further ion accumulation. Each MS module comprises one IB-channel. Depending on the type of dispersing analyzer IB-channel, different MS versions comprise a different number of detector modules and outputs to them. The Makarov reference (trapping distribution module) is mainly used as a dispersing analyzer IB-channel. Additionally, this prior invention teaches other versions of dispersing analyzer IB-channel embodiment, e.g. in a multi-reflecting mode.
The Makarov prototype is notable for its high weighing precision in multi-reflecting mode up to <2 ppm (at internal calibrations). It has resolution power over 100000. Such a device costs several millions of US$.
The main disadvantage of this prototype is in low value of resolution power/costs ratio (marginal costs). It provides no MS versions assuring flexible configuration modification for specific tasks through varied levels of block-structured docking group modularity. Moreover, this prototype does not consider species of electric (nonmagnetic) time-of-flight (TOF) IB-channels and their characteristics promising to enhance values of resolution power/costs ratios.
Values of the resolution power/costs ratio and the MS power potentials are determined mainly by the MS modularity level as well as by the functional characteristics and by the cost of IB-channels (especially by the resolution power of dispersing analyzer IB-channel and the IB-channel of ion trapping, if any) suitable for assembly of such modules.
The MS with different modularity levels are commonly based on use of electric IB-channels of multi-resolution modes, such as nonmagnetic static electric fields or electric fields with variable components, by virtue of the resolution power/costs ratio in their operations as IB-channels of ions trapping and mass dispersing analyzer IB-channel. A nonmagnetic/electric IB-channel differs from other types of IB-channels (e.g., with double focusing, ion cyclotron resonance, sectoral-magnetic, Fourier analyzers etc.) by smaller geometrical dimensions, masses and power capacity, and by a simple and reliable design. Moreover they are relatively cheap. E.g., nonmagnetic time-of-flight MS (TOF MS) based on the electric time-of-flight IB-channel surpasses other MS types by its unlimited mass ranges (up to tens of millions of atomic mass) and higher analysis rates. These TOF MS functional capabilities allow to carry out analyses unreachable by means of other types of mass-spectrometers, e.g., analyze time-varying processes or organic matters which are mixtures of different individual compounds (e.g., oil).
Currently there are known electric TOF IB-channels used in MS, which may be classified by four main resolution levels, i.e.: first resolution level specifies the radio frequency TOF IB-channels of linear type (variable fields) and of electrostatic type with a straight main optical axis (static fields); second resolution level specifies the reflectron TOF IB-channels (with straight main optical axis and single-reflecting channels); third resolution level specifies the reflectron TOF IB-channels with a curved main axis (including single-, double-, and triple-reflection subsystems with a curve axis or reflection-refraction subsystem) and having vectors of input and output path ion flux spaced from each other; fourth resolution level specifies the multi-reflecting TOF IB-channels (over five reflections).
There are known linear radio frequency (variable fields) and electrostatic with straight main optical axis (static fields) TOF IB-channels used in different linear TOF MS (s-TOF MS)—such as AXIMA-LNR [www.analyt.ru], MSX-4 [www.niivt.ru] and those described in patent RU 2367053. In linear radio frequency IB-channels (e.g., RU 2367053) plate electrodes generating periodic two-dimensional linear high frequency (HF) fields are provided along the axis between ions source and ions detector. HF fields step up the path and time of ion movement in the TOF MS, enhancing ions dispersion by masses (i.e., enhancing MS resolution capacity) as compared to electrostatic IB-channels with a straight main optical axis (static fields).
Linear TOF IB-channels in the TOF MS provide only a low resolution level (resolution reaches some hundreds), but they are small-sized, simple in operations, and power and cost saving.
There are known reflectron TOF IB-channels (e.g.: RF patent No. 2 103 763 C, Publ. 27 Jan. 1998; U.S. Pat. No. 4,694,168, Publ. 15 Sep. 1987) used in the reflectron TOF MS (sR-TOF MS) where the area of all operating processes of ion flux covers the TOF MS straight main axis. The reflectron IB-channel in each such sR-TOF MS comprises a special area of a single reflection of ion packages within an electric field. Reflection of an ion package is used to enhance resolution power through time-of-flight focusing of the ion package by ionic energy. As with all known patents and manufactured devices related to the sR-TOF MS, in order to reflect ion packages there are applied uniform electric fields enclosed by one or several fine-meshed metal screens.
A method of single-reflecting spectrometry with straight main optical axis based on the reflectron IB-channel consists of directing ion packages towards one or several electric fields, enclosed by screens, at a right angle to the mesh planes, reflection of the ion packages throughout the electric fields and further ion package logging. As such, along the path from the source to the detector, ion packages pass twice through each screen required to generate electric fields commonly considered as uniform.
Reflectron IB-channels in a sR-TOF MS provide a mean resolution level (resolution reaches up to several thousand), while they are small-sized, simple in operations, and power- and cost saving.
The main sR-TOF MS disadvantage is in the relatively low resolution power due to the fact that the fine-mesh screens located in the area of ion movement give rise to several phenomena adversely affecting the performance characteristics of reflectron IB-channels, in particular, to ions scattering at the screens and uncontrolled extra ionic energy spread, and consequently, to lowering of IB-channel resolution power.
There are known reflectron TOF MSs (cR-TOF MS) comprising IB-channels with ion flux axes spaced from each other (for spaced source and detector) and with a curved main axis (e.g.: U.S. Pat. No. 6,621,073, B1, Publ. 16 Sep. 2003; US, 2008/0272287 A1, Publ. 6 Nov. 2008).
Methods described in the above mentioned patents consist of operation of an IB-channel with one to three reflecting electric fields and direction of ion packages emitted by a source into these reflecting electric fields at acute angles relatively to vectors of the fields; of ion packages reflecting in the electric fields; and further of ion packages logging.
In U.S. Pat. No. 6,621,073, B1 and US patent 2008/0272287 A1 the IB-channels comprise uniform electrostatic or reflector fields enclosed by one or several close-mesh screens extended at slit diaphragms. In US patent 2008/0272287 A1, the diaphragms and detector slits are sized considering that the width of a reflected ion package is greater than its width when incoming due to different ionic energy in the package.
There is known a single-reflecting and triply-reflecting embodiment of an IB-channel used in cR-TOF MSs (U.S. Pat. No. 6,717,132 B2, Publ. Apr. 6, 2004), specifying gridless reflector fields generated by slit diaphragms for single-triple reflections. Herein it is assumed that the field of slit diaphragms within an area of ion flux passage is a Cartesian-two-dimensional field, in which no forces act on the ions in a horizontal direction.
The main disadvantage of the IB-channel with a Cartesian-two-dimensional field consists in the default of focusing ions in a direction parallel to the middle plane and in a slit that gives rise to ion scattering, and consequently, to lowering of resolution power of the cR-TOF MS including with such an IB-channel.
The known cR-TOF MSs operate in a resolution ranging from several thousands to several tens of thousands depending on their design, though the average sensitivity level is equal to 10−4.
There are known IB-channels having a curved main axis in a cross-space dispersing mode with two-dimensional electric and/or magnetic fields, e.g. V-shaped or conic, (papers of Spivak, Lavrov I. F. and others) in expressly selected coordinates. There are known the IB-channels having a curved main axis in a cross-space dispersing mode with Cartesian-two-dimensional electric and magnetic (prismatic) fields (papers of Kelman V. M., Yakushev E. M. and others.). The main disadvantage of such IB-channels is in a low value of resolution power/costs ratio.
There is known a multi-reflecting MS with an IB-channel comprising a channel IO subsystem of multi-reflector type (oMR-TOF MS) configured for single rectilinear reflecting mode and including a stepped R-multi-reflector of narrow form (certificate of authorship SU 1725289 A1 dated 7 Apr. 1992, Bulletin No. 13). A stepped R-multi-reflector of narrow form is designed to provide potential ion movement through the paths whose projections on the R-multi-reflector base plane are approximately linear segments. A stepped R-multi-reflector of narrow form comprises two single-zone extended reflector R-modules of a Cartesian-two-dimensional type arranged opposite one another when their axial vectors are anti-parallel and are located in the same plane (in a M-plane of R-multi-reflector), where their axial lines are parallel to each other and perpendicular to the R-multi-reflector base plane. Ions are subjected to multiple reflections between single-zone extended Cartesian-two-dimensional R-reflectors. As such, the ions slowly drift towards the detector in a drift direction moving towards the linear axes of the extended reflector R-modules located in a longitudinal R-multi-reflector plane. The number of cycles and resolution level are corrected through modifications of the ion injection angle.
The description of the mentioned certificate of authorship discloses theoretical principles of MR-TOF MS performance analysis and computation.
Disadvantages of the mentioned cR-TOF MS designs and operations are in the default of focusing along the parallel longitudinal-incremental plane of R-multi-reflector. When an ion flux traverses certain tracks along the parallel longitudinal-incremental plane of R-multi-reflector the dispersion of ion flux reaches values rendering the attempts to detect mass spectrum meaningless.
U.S. Pat. No. 7,385,187 B2; Jun. 10, 2008 developing concepts of authorship certificate SU 1725289 A1, of 7 Apr. 1992, Bull. No. 13, proposes to provide an electrostatic lens in the IB-channel between two periodic single-zone extended R-reflection units of a Cartesian-two-dimensional type. An electrostatic lens allows directing ion packages along the linear axes (in a longitudinal-incremental plane) of the extended reflector R-modules. Such an analyzer allows retaining permanent ion fluxes within long-distance span lengths and enhancing TOF ions dispersion by mass while providing low space and time aberrations, thus achieving a high resolution power.
U.S. Pat. No. 7,385,187 B2 also describes the principle of parallel tandem time-of-flight analysis in an “embedded times” mode, substantially enhancing the efficiency of complex biopolymer mixture analysis.
Experimental oMR-TOF MS studies (Verenchikova A. Abstract of PhD thesis, St. Petersburg, 2006) demonstrate high resolution power exceeding 200000 of the analyzer as described in U.S. Pat. No. 7,385,187 B2.
US patent 2010/008386 A1, Publ. Jan. 11, 2010, developing concepts of U.S. Pat. No. 7,385,187 B2; Jun. 10, 2008, proposes for a single rectilinear reflector IB-channel of multi-reflecting mode extended R-reflection units to provide periodic modulations of electrostatic fields along the longitudinal-incremental propagation of an ion flux, for the purpose of periodical space focusing of ion packages. In addition to this periodic modulation of electrostatic fields there is provided at least one isochronic curve of an interface surface between a pulsed ion source and a receiver in the MS.
One of the most serious disadvantages of known oMR-TOF MSs is in direct multicycle operation mode required to achieve high resolution power in the IB-channel with an IO channel subsystem configured as a single multireflector. In such IB-channels the paths of extended ions fluxes have multiple intersections that lead to Coulomb ions scattering, desensitization and decreased oMR-TOF MS resolution power; lighter ions may go ahead of heavier ions by one and more cycles, resulting in obtained mass spectrum multiplicity; extended R-reflectors with isochronic curved surfaces are used in addition to periodic modulations of electrostatic fields, even though each of them may be used individually.